This explanation helps if you know that two finite-dimensional vector spaces over the same field, $F$, are isomorphic if and only if they have equal dimensions.
If you're using Sheldon Axler's Linear Algebra Done Right (3rd. Edition), you might have seen $\mathcal{L}(V,W)$ as a domain in the context of using the linear map $\mathcal{M}$, which maps $\mathcal{L}(V,W)$ to $F^{mn}$, where $F^{mn}$ is the set of all m-by-n matrices, where each entry is in $F$.
Formally:
$\mathcal{M} : \mathcal{L}(V,W) \rightarrow F^{mn}$
So using the Fundamental Theorem of Linear Maps, we know that:
dim $\mathcal{L}(V,W) =$ dim null $\mathcal{M}$ $+$ dim range $\mathcal{M}$
So our goal now is to prove that: dim $\mathcal{L}(V,W) =$ (dim $V$)(dim $W$)
Let's start with a basis $v_1, ..., v_n$ for $V$ and a basis $w_1, ..., w_m$ for a basis of W. This means that dim $V = n$ and dim $W = m$. And this also makes sense because $\mathcal{M}(T)$, where $T \in \mathcal{L}(V,W)$, represents an m-by-n matrix that holds the coefficients for the basis of $W$ to make $Tv_k$:
$Tv_k = A_{1,k}w_1 + A_{2,k}w_2 + ... + A_{m,k}w_m$, where $A_{j,k}$ are entires of the k-th column of $\mathcal{M}(T)$ for $1 \leq j \leq m$
If you need help convincing yourself that dim $F^{mn} = mn =$ (dim $V$)(dim $W$), just imagine the basis of $F^{mn}$ to be a list of m-by-n matrices where each matrix has entries of all $0$'s except one where there is a $1$:
$\begin{equation}
\begin{bmatrix}
1 & 0 & \ldots & 0\\
0 & 0 & \ldots & 0\\
\vdots & \ldots & \ldots & 0\\
0 & \ldots & \ldots & 0\\
\end{bmatrix},
\
\begin{bmatrix}
0 & 1 & \ldots & 0\\
0 & 0 & \ldots & 0\\
\vdots & \ldots & \ldots & 0\\
0 & \ldots & \ldots & 0\\
\end{bmatrix},
\
\ldots , \
\
\begin{bmatrix}
0 & 0 & \ldots & 0\\
0 & 0 & \ldots & 0\\
\vdots & \ldots & \ldots & 0\\
0 & \ldots & \ldots & 1\\
\end{bmatrix}
\end{equation}$
We see that there are a total of $mn$ matrices in the basis of $F^{mn}$.
Now, in order for dim $\mathcal{L}(V,W) = mn =$ (dim $V$)(dim $W$), we need to show that dim $\mathcal{L}(V,W) = $ dim $F^{mn}$. So that means that we need to show that dim null $\mathcal{M} = 0$ and dim range $\mathcal{M} = $ dim $F^{mn}$ (in other words, show that $\mathcal{M}$ is injective and surjective).
To show that $\mathcal{M}$ is injective, we need to show that $\mathcal{M}(T) = 0$, where $T = 0$. In order to do so, let's suppose that $\mathcal{M}(T) = 0$, where $0$ is the m-by-n matrix that has all entries as $0$. What this means is that: $Tv_k = 0$ because:
$Tv_k = 0w_1 + 0w_2 + ... + 0w_m$
Since $v_k$ is an element from the basis of $V$, $v_k \neq{0}$, therefore $T = 0$. Hence, null $\mathcal{M} = \{0\}$ and thus dim null $\mathcal{M} = 0$.
So what we have now is dim $\mathcal{L}(V,W) = $ dim range $\mathcal{M}$, where we need to show that range $\mathcal{M} = F^{mn}$.
Let's suppose that $A \in F^{mn}$. Remember that:
$Tv_k = A_{1,k}w_1 + A_{2,k}w_2 + ... + A_{m,k}w_m$, where $A_{j,k}$ are entires of the k-th column of $\mathcal{M}(T)$ for $1 \leq j \leq m$
So, we see that $\mathcal{M}(T) = A$. By using the element-method, we see that range $\mathcal{M} \subseteq F^{mn}$ and $F^{mn} \subseteq$ range $\mathcal{M}$, thus range $\mathcal{M} = F^{mn}$.
Therefore, dim $\mathcal{L}(V,W) = $ dim $F^{mn} = mn = $ (dim $V$)(dim $W$).
As we see, we showed that because these two vector spaces are isomorphic, they possess equal dimensions.